JP6214533B2 - Ion trap with a spatially expanded ion trap region - Google Patents

Description

  The present invention relates to a selective ion trap of mass or mass to charge ratio. Preferred embodiments relate to methods for use in ion guide and ion trapping systems and mass spectrometry systems.

CROSS REFERENCE TO RELATED APPLICATIONS This application is based on US Provisional Application No. 61 / 528,956 filed on Aug. 30, 2011 and British Patent Application No. 111474.5 filed on Aug. 25, 2011. Insist on priority and interests. The entirety of these applications is incorporated herein by reference.

  It is well known that the time average force on charged particles or ions due to a non-uniform AC electric field is such that the electric field accelerates the charged particles or ions to a weaker region. The minimum in the electric field is commonly called a pseudopotential well or valley. In contrast, the local maximum is commonly referred to as a pseudopotential hill or barrier.

  Pole traps, also known as three-dimensional ion traps, are designed to take advantage of this phenomenon by forming a pseudopotential well in the center of the ion trap. Pseudopotential wells are used to confine ion populations. Due to its symmetry, the three-dimensional ion trap acts to confine ions to a single point in space as shown in FIG. 1A. However, in addition to the non-zero kinetic energy of the confined ions, the repulsion between ions of the same polarity causes the ions to occupy a spherical volume at the center of the ion trap, as shown in FIG. 1B.

  There is a finite space charge capacity for any ion confinement device, beyond which its performance begins to degrade and eventually the device cannot hold any further charge. For example, supersaturation of an ion trap leads to loss of mass resolution and mass accuracy as a result of the electric field being distorted by the presence of a large number of charges focused in the vicinity. It is generally true that the space charge limit for ion accumulation is significantly greater than the spectral or analytical space charge limit, which is the maximum number of ions that can be confined while maintaining a given mass resolution and mass accuracy.

  In mass spectrometry applications, it is necessary to detect the mass-to-charge ratio (m / z) of trapped ions. For example, ions may be ejected mass selective towards an ion detector (but there are many other detection methods). There are several known methods for ejecting ions, either resonant or non-resonant, to achieve this goal.

  It is often necessary to introduce gas into the ion trap device. The gas may be used for cooling purposes or for ion fragmentation via Collision Induced Dissociation (“CID”). Ion Mobility Separation (“IMS”) has also been performed in either a static volume of gas or a flow of gas. The use of pulse gas valves to introduce gas into the ion trap is also known.

  Recently, interest in two-dimensional or linear ion traps (“LIT”) has increased due to the large volume that can be occupied by trapped ions. A linear ion trap allows a larger number of ions, or more precisely a larger number of charges, to be confined and then detected. Such ion traps are generally based on multipole RF ion guides such as quadrupole, hexapole, or octupole. A pseudo-potential well is formed in the rod set ion trap around the central axis of the ion guide so that ions are confined radially within the ion trap. Ions are usually confined axially using a DC electric field, but methods using an RF electric field to confine ions in the axial direction are also known.

  The radial pseudopotential of the two-dimensional ion trap acts to focus the trapped ions into a line that passes through the central axis of the ion trap as shown in FIG. 1C. Similar to the three-dimensional ion trap, ions confined within the two-dimensional ion trap will actually be spatially dispersed and thus occupy an elongated cylindrical volume, as shown in FIG. 1D.

  Ion emission has been demonstrated both radially and axially using a two-dimensional ion trap by resonantly exciting ions in a radial confinement pseudopotential. Radial ejection is achieved by causing the ions to resonate until the radial extent of the ions reaches the quadrupole electrode, where the ions pass through a narrow slot in the electrode. Axial ejection is achieved by resonantly exciting ions into a naturally occurring fringe field at the exit of the quadrupole, where the ion has enough axial kinetic energy to overcome the confined DC barrier. Has been achieved. Both of these methods are inherently non-adiabatic, leading to high emission energy and high energy diffusion, which is generally unsuitable for coupling them with other devices such as other mass spectrometers. Make things.

  Another form of axial emission from a two-dimensional ion trap is known, which involves superimposing an axial harmonic DC potential on the radial confinement RF of the ion guide. Such an approach is schematically represented in FIGS. 2A-2C.

  FIG. 2A shows a two-dimensional ion trap comprising a series of annular electrodes that coaxially surround a quadrupole rod set. An RF voltage is applied to the rod set electrode to confine ions in the radial direction. A DC voltage is applied to the annular electrode to create an axial DC potential within the rod set.

  FIG. 2B shows a two-dimensional ion trap comprising an RF quadrupole rod set with an additional vane electrode placed on the ground plane used to provide an axial DC potential.

  FIG. 2C shows a two-dimensional ion trap comprising an axially segmented RF quadrupole rod set. Different DC voltages may be applied to each segment to provide an axial DC potential.

  For the two-dimensional ion trap shown in FIGS. 2A-2C, the DC potential applied in the axial (z) direction is given by Equation 1.

According to one aspect of the invention,
A first device arranged and adapted to generate a radially asymmetric pseudopotential barrier or well that serves to confine ions in a first (y) and second (x) directions within the ion trap; ,
A second device arranged and adapted to generate a substantially DC potential well that serves to confine ions in a third (z) direction within the ion trap, wherein the second device is substantially a quadrupole DC current. The second device, wherein the profile of the position changes gradually along the second (x) direction;
Arranged to excite ions in the third (z) direction so as to selectively eject ions of mass or mass to charge ratio in the second (x) direction and / or the third (z) direction A mass or mass-to-charge ratio selective ion trap comprising a third device adapted and adapted.

According to one aspect of the invention,
Arranged to generate a pseudopotential barrier or well that acts to confine ions in the first (y) direction within the ion trap, and a DC potential barrier or well that acts to confine ions in the second (x) direction. A first device adapted and adapted;
A second device arranged and adapted to generate a substantially dc quadrupole potential well that serves to confine ions in a third (z) direction within the ion trap, wherein the second device is substantially quadruple. The polar DC potential profile gradually changes along the second (x) direction;
Arranged to excite ions in the third (z) direction so as to selectively eject ions of mass or mass to charge ratio in the second (x) direction and / or the third (z) direction A mass or mass-to-charge ratio selective ion trap comprising a third device adapted and adapted.

  The first (y) direction and / or the second (x) direction and / or the third (z) direction are preferably substantially orthogonal.

  According to one embodiment, the mass or mass to charge ratio selective ion trap includes a plurality of electrodes.

Multiple electrodes
(I) Multiple or at least 4, 5, 6, 7, 8, 9, 10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80 -90, 90-100 or more than 100 rod sets or segmented rod sets, multipole rod sets or segmented multipole rod sets, and / or
(Ii) a plurality or at least 4, 5, 6, 7, 8, 9, 10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80 ~ 90, 90-100 or more than 100 annular, ring, or oval electrodes, with one or more apertures through which ions pass through in use, annular, ring, or oval An ion tunnel or ion funnel containing electrodes, and / or
(Iii) a plurality or at least 4, 5, 6, 7, 8, 9, 10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80 ~ 90, 90-100 or more than 100 semi-annular, semi-ring, semi-oval, or C-shaped electrodes, and / or
(Iv) It is preferable to include a plane electrode, a plate electrode, or a laminate or array of mesh electrodes that are generally arranged on a plane in which ions move when used.

  The first device is preferably arranged and adapted to apply a high frequency voltage to at least some of the electrodes.

  The ion trap is preferably arranged and adapted so that there is a solid and / or straight perspective line of the ion trap in the third (z) direction.

  The ion trap is preferably arranged and adapted so that there is a solid and / or straight perspective line of the ion trap in the second (x) direction.

  The second device is that (i) the minimum of the quadrupole DC potential well is along the central axis of the ion trap, or (ii) the minimum of the quadrupole DC potential well is substantially It is preferably arranged and adapted to form a substantially quadrupole DC potential well so as to be offset from the central axis of the trap.

  The pseudopotential barrier or well preferably comprises a non-quadrupole pseudopotential barrier or well.

  The third device is preferably arranged and adapted to vibrate the ions in the third (z) direction, the amplitude of the ion vibration in the third (z) direction being the mass or mass of the ions. Preferably it depends on the charge-to-charge ratio.

  The electric field is preferably maintained along the second (x) direction.

  The electric field preferably increases, decreases or changes gradually along the second (x) direction.

  The electric field preferably drives, flows or directs ions toward the ion emission region of the ion trap. Preferably, ions are selectively ejected from the ion emission region in the second (x) direction and / or the third (z) direction in mass or mass to charge ratio.

  The magnitude of the electric field in the second (x) direction is preferably increased, decreased or changed depending on the position in the third (z) direction.

  The electric field preferably causes the ions to experience a substantially different acceleration field in the second (x) direction, depending on the relative position of the ions in the third (z) direction.

  The electric field may cause ions having a particular mass or mass-to-charge ratio, or second mass or mass-to-charge ratio, to selectively eject ions of mass or mass-to-charge ratio in the third (z) direction. It is preferable to promote ions having a specific range in the direction (x).

  The electric field is applied to the vibration of the ions in the third (z) direction before selectively ejecting ions of mass or mass to charge ratio in the second (x) direction and / or the third (z) direction. The ions are preferably propelled in the second (x) direction with a force that depends on the amplitude.

  It is preferable to confine ions in the third (z) direction by a DC quadrupole potential well, and ions having vibration amplitude in the third (z) direction are separated from the emission region in the second (x) direction. Ions in the emission region that are confined by the ion trap in the selected region while having the same amplitude of vibration in the third (z) direction can cross the DC potential well and be ejected from the ion trap. In addition, the height of at least one side surface of the well is preferably decreased depending on the position in the second (x) direction toward the emission region.

  The second device is preferably arranged and adapted to maintain a substantially dc quadrupole potential well across all but not all of the electrodes arranged in the third (z) direction. .

  The second device is preferably arranged and adapted to maintain a substantially dc quadrupole potential well across x% of the width of the ion trap in the third (z) direction. However, x is (i) less than 10, (ii) 10-20, (iii) 20-30, (iv) 30-40, (v) 40-50, (vi) 50-60, (vii) 60 -70, (viii) 70-80, (ix) 80-90, (x) 90-95, and (xi) 95-99.

  The second device is preferably arranged and adapted to maintain a DC potential profile in a third (z) direction across the ion trap, the DC potential profile being in the first region and the one or more second. The DC potential profile in the first region is substantially quadrupole and the DC potential profile in the one or more second regions is substantially linear, constant, or Non-quadrupole.

  The second device is preferably arranged and adapted to maintain a DC potential profile in the third (z) direction, preferably asymmetric with respect to the central axis of the ion trap, the central axis preferably It is in the second (x) direction.

  The second device is preferably arranged and adapted to maintain a DC potential profile in the third (z) direction, so that ions are substantially ejected from the DC quadrupole well in only one direction. .

  A third device selectively ejects ions from the ion trap either (i) in the first direction only, or (ii) in either the first direction or the second direction, in mass or mass-to-charge ratio. Preferably, the second direction is different from or opposite to the first direction.

  The third device is preferably arranged and adapted to resonantly excite ions in the third (z) direction.

  The third device is preferably arranged and adapted to apply an auxiliary AC voltage or auxiliary AC potential to at least some of the electrodes having a frequency σ equal to ω, where ω is preferably emitted from the ion trap. It is the fundamental frequency or resonance frequency of ions.

  The third device is preferably arranged and adapted to parametrically excite ions in the third (z) direction.

  The third device has an auxiliary AC voltage or auxiliary AC potential at a frequency equal to or less than 2ω, 0.667ω, 0.5ω, 0.4ω, 0.33ω, 0.286ω, 0.25ω. Preferably, it is arranged and adapted to be applied to at least some of the electrodes having σ, where ω is the fundamental or resonant frequency of the ions that it is desired to eject from the ion trap.

  The third device is preferably arranged and adapted to scan, change, modify, increase, gradually increase, decrease or gradually reduce the frequency σ of the auxiliary AC voltage or auxiliary AC potential. .

  The third device is (i) in an operating mode for ejecting ions from the ion trap in the order of ion mass-to-charge ratio and / or (ii) ions from the ion trap in reverse order of ion mass-to-charge ratio It is preferably arranged and adapted to the mode of operation for releasing.

  The third device is preferably arranged and adapted to eject ions from the ion trap in a substantially adiabatic manner.

  The third device is (i) less than 0.5 eV, (ii) 0.5-1.0 eV, (iii) 1.0-1.5 eV, (iv) 1.5-2.0 eV, (v) 2.0-2.5 eV, (vi) 2.5-3.0 eV, (vii) 3.0-3.5 eV, (viii) 3.5-4.0 eV, (ix) 4.0-4. It is preferably arranged and adapted to emit ions from the ion trap with an ion energy selected from the group consisting of 5 eV, (x) 4.5-5.0 eV, and (xi) an energy exceeding 5.0 eV. .

Ion trap, it is preferred to be adapted is arranged to include the N ionic charge in the ion trap, N is (i) 5x10 less than ^{4, (ii) 5x10 4 ~1x10} 5, (iii) 1x10 5 ^{~2x10 5, (iv) 2x10 5} ~3x10 5, (v) 3x10 5 ~4x10 5, (vi) 4x10 5 ~5x10 5, (vii) 5x10 5 ~6x10 5, (viii) 6x10 5 ~7x10 5, ( ^{ix) 7x10 5 ~8x10 5, (} x) 8x10 5 ~9x10 5, is selected from the group consisting of (xi) 9x10 ⁵ ~1x10 ⁶ and (xii) number of greater than 1x10 ^6.

In the mode of operation, at least a region or substantially the entire ion trap is
(I) as an ion guide and / or
(Ii) as a collision cell or fragmentation cell and / or
(Iii) as a reaction cell and / or
(Ii) as a mass filter and / or
(Iii) as a time-of-flight separator and / or
(Iv) as an ion mobility separator and / or
(V) It is preferably arranged and adapted to operate as a differential ion mobility separator.

In the mode of operation, the ion trap is (i) less than 1.0 × 10 ⁻⁷ mbar, (ii) 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁶ mbar, (iii) 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mbar. (Vi) 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻⁴ mbar, (v) 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻³ mbar, (vi) 0.001 to 0.01 mbar, (vii) 0.01 -0.1 mbar, (viii) 0.1-1 mbar, (ix) 1-10 mbar, (x) 10-100 mbar, and (xi) maintained at a pressure selected from the group consisting of 100-1000 mbar Preferably adapted.

  In accordance with one aspect of the present invention, a mass analyzer is provided that includes a selective ion trap of mass or mass to charge ratio as described above.

According to one aspect of the invention,
Generating a radially asymmetric pseudopotential barrier or well that serves to confine ions in a first (y) direction and a second (x) direction within the ion trap;
Generating a substantially DC quadrupole potential well that acts to confine ions in the third (z) direction within the ion trap, wherein the profile of the quadrupole DC potential well is substantially Occurring gradually along the direction of 2 (x);
Exciting the ions in the third (z) direction to selectively eject ions of mass or mass to charge ratio in the second (x) direction and / or the third (z) direction. A method is provided for selectively ejecting ions from a mass trap or mass to charge ratio from an ion trap.

According to one aspect of the invention,
A pseudopotential barrier or well that acts to confine ions in the first (y) direction within the ion trap and a DC potential barrier or well that acts to confine ions in the second (x) direction are generated. And
Generating a substantially DC quadrupole potential well that acts to confine ions in the third (z) direction within the ion trap, wherein the profile of the quadrupole DC potential well is substantially Occurring gradually along the direction of 2 (x);
Exciting ions in the third (z) direction to selectively eject mass or mass-to-charge ratio ions from the ion trap in the second (x) direction and / or the third (z) direction A method of selectively releasing ions of mass or mass to charge ratio from an ion trap.

  According to one aspect of the present invention, there is provided a mass spectrometry method comprising the method as described above.

  According to one aspect of the present invention, spatially into a two-dimensional space, ions of a selected mass-to-charge ratio move from the total volume to a smaller emission region before the ions are ejected from the ion trap. An ion trap with an expanded trapping volume is provided.

  Despite the larger capacity of the two-dimensional ion trap than the three-dimensional ion trap, the need for increasing the ion trap's ion capacity increases as the instrument becomes more sensitive and the ion source becomes brighter.

  Preferred embodiments include ion trap devices or ion permeation devices with an enlarged trapping volume or permeation volume. According to one embodiment, the ion trap includes a one-dimensional ion trap that is arranged to confine and eject ions and has a larger ion charge capacity than a conventional three-dimensional ion trap and a two-dimensional ion trap.

  Similar to the three-dimensional ion trap confining ions basically to one point and the two-dimensional ion trap basically confining ions to one line, the one-dimensional ion trap according to the preferred embodiment is as shown in FIG. 1E. Basically, ions are confined to one surface. In practice, however, the actual volume occupied by the ions is expanded to fill the two-dimensional space with an elongated cuboid as shown in FIG. 1F.

  An ion trap according to a preferred embodiment of the present invention includes an array of electrodes defining an enlarged volume to which various combinations of high frequency voltage, AC voltage and DC voltage can be applied. The ion trap may act as an ion permeation device or as an ion trap. An ion trap may be used to hold, stack, store, process, sequester, fragment, detect, and release ions. In operation, some or all of the ions are dispersed within the enlarged trap region, and subsequently depend on the mass-to-charge ratio from the ion trap to the specific region of the ion trap where ions can be ejected. May be moved. The release of ions is preferably influenced by exciting the ions substantially within the DC quadrupole potential. The shape of the quadrupole potential varies with the length of the device so that the shape of the quadrupole potential is steeper in some regions and narrower in other regions. Due to the action of exciting the ions, the ions are squeezed from a steeper region to a narrower region where the ions are eventually released.

  The ion trap may operate as a mass analyzer or may be used in conjunction with a mass analyzer or other device within the mass spectrometer.

According to one embodiment, the mass spectrometer is
(A) (i) electrospray ionization (“ESI”) ion source, (ii) atmospheric pressure photoionization (“APPI”) ion source, (iii) atmospheric pressure chemical ionization (“APCI”) ion source, (iv) Matrix-assisted laser desorption ionization (“MALDI”) ion source, (v) laser desorption ionization (“LDI”) ion source, (vi) atmospheric pressure ionization (“API”) ion source, (vii) on-silicon desorption Ionization (“DIOS”) ion source, (viii) electron impact (“EI”) ion source, (ix) chemical ionization (“CI”) ion source, (x) field ionization (“FI”) ion source, (xi ) Field desorption (“FD”) ion source, (xii) inductively coupled plasma (“ICP”) ion source, (xiii) fast atom bombardment (“FAB”) ion source, (xiv) liquid two Ion mass spectrometry (“LSIMS”) ion source, (xv) desorption electrospray ionization (“DESI”) ion source, (xvi) nickel 63 radioactive ion source, (xvii) atmospheric pressure matrix assisted laser desorption ionization ion source, An ion source selected from the group consisting of (xviii) a thermospray ion source, (xix) an atmospheric sampling glow discharge ionization (“ASGDI”) ion source, and (xx) a glow discharge (“GD”) ion source, and / or Or
(B) one or more continuous or pulsed ion sources and / or
(C) one or more ion guides and / or
(D) one or more ion mobility separators and / or one or more field asymmetric ion mobility analyzers, and / or
(E) one or more ion traps or one or more trapping regions, and / or
(F) (i) collision induced dissociation (“CID”) fragmentation device, (ii) surface induced dissociation (“SID”) fragmentation device, (iii) electron transfer dissociation (“ETD”) fragmentation device, (iv) electron capture Dissociation ("ECD") fragmentation device, (v) electron impact or impact dissociation fragmentation device, (vi) photoinduced dissociation ("PID") fragmentation device, (vii) laser induced dissociation fragmentation device, (viii) infrared induced dissociation device (Ix) UV-induced dissociation device, (x) nozzle skimmer interface fragmentation device, (xi) in-source fragmentation device, (xii) in-source collision-induced dissociation fragmentation device, (xiii) heat source or temperature source frame Fragmentation device, (xiv) electric field induced fragmentation device, (xv) magnetic field induced fragmentation device, (xvi) enzymatic digestion or enzymatic fragmentation device, (xvii) ion-ion reaction fragmentation device, (xviii) ion-molecule reaction fragmentation device (Xx) ion-atom reaction fragmentation device, (xx) ion-metastable ion reaction fragmentation device, (xxi) ion-metastable atom reaction fragmentation device, (xxii) ion-metastable atom reaction fragmentation device, (xxiii) An ion-ion reactor that forms adduct ions or product ions by reaction of ions, (xxiv) addition ions or product ions by reaction of ions An ion-molecule reaction device that forms, an ion-atom reaction device that forms addition ions or product ions by reaction of (xxv) ions, and an ion-metastable ion reaction that forms addition ions or product ions by reaction of (xxvi) ions An apparatus, (xxvii) an ion-metastable molecular reactor that forms adduct ions or product ions by reaction of ions, (xxviii) an ion-metastable atom reactor that forms adduct ions or product ions by reaction of ions, and ( xxix) one or more collisions, fragmentation or reaction cells selected from the group consisting of electron ionization dissociation (“EID”) fragmentation devices, and / or
(G) (i) quadrupole mass analyzer, (ii) two-dimensional or linear quadrupole mass analyzer, (iii) pole-type or three-dimensional quadrupole mass analyzer, (iv) Penning trap type mass Analyzer, (v) ion trap mass analyzer, (vi) magnetic sector sector mass analyzer, (vii) ion cyclotron resonance ("ICR") mass analyzer, (viii) Fourier exchange ion cyclotron resonance ("FTICR") ) Mass analyzer, (ix) electrostatic or orbitrap mass analyzer, (x) Fourier exchange electrostatic or orbitrap mass analyzer, (xi) Fourier exchange mass analyzer, (xii) time-of-flight mass spectrometry A mass analyzer selected from the group consisting of: a (xiii) orthogonal acceleration time-of-flight mass analyzer; and (xiv) a linear acceleration time-of-flight mass analyzer, and / or ,
(H) one or more energy analyzers or electrostatic energy analyzers, and / or
(I) one or more ion detectors and / or
(J) (i) quadrupole mass filter, (ii) two-dimensional or linear quadrupole ion trap, (iii) pole-type or three-dimensional quadrupole ion trap, (iv) Penning ion trap, (v) One or more mass filters selected from the group consisting of ion traps, (vi) magnetic sector mass filters, (vii) time-of-flight mass filters, and (viii) Wien filters, and / or
(K) a device or ion gate for pulsing ions and / or
(L) The apparatus may further comprise an apparatus for converting a substantially continuous ion beam into a pulsed ion beam.

Mass spectrometer
(I) an orbitrap type (RTM) mass analyzer comprising a C-type trap and an outer barrel electrode and a coaxial inner spindle electrode, in a first mode of operation, ions are transmitted through the C-type trap and then Injected into an orbitrap type (RTM) mass analyzer, in the second mode of operation, ions are transmitted to a C-type trap and then to a collision cell or electron transfer dissociator and at least some ions are fragmented into fragment ions Fragment ions are transmitted through a C-type trap and then injected into an Orbitrap (RTM) mass analyzer, and / or an Orbitrap (RTM) mass analyzer, and / or
(Ii) a stacked annular ion guide comprising a plurality of electrodes each having an aperture through which ions are transmitted when in use, the spacing of the electrodes increasing along the length of the ion path; The opening of the electrode disposed in the upstream portion has a first diameter, and the opening of the electrode disposed in the downstream portion of the ion guide has a second diameter smaller than the first diameter, and the alternating current is in use. The anti-phase of the voltage or the high-frequency voltage may further include either a laminated annular ion guide that is applied to a continuous electrode.

  The high frequency voltage is preferably applied to a preferred ion trap electrode, (i) less than 50V peak-to-peak, (ii) 50-100V peak-to-peak, (iii) 100-150V peak-to-peak, (iv) 150 ~ 200V peak-to-peak, (v) 200-250V peak-to-peak, (vi) 250-300V peak-to-peak, (vii) 300-350V peak-to-peak, (viii) 350-400V peak-to-peak, (ix) 400 ~ 450V peak-to-peak, (x) 450-500V peak-to-peak, (xi) 500-550V peak-to-peak, (xxii) 550-600V peak-to-peak, (xxiii) 600-650V peak-to-peak, (xxiv) 650 ~ 700V peak to peak, (xxv) 700-750V peak-to-peak, (xxvi) 750-800V peak-to-peak, (xxvii) 800-850V peak-to-peak, (xxviii) 850-900V peak-to-peak, (xxix) 900-950V peak-to-peak, Preferably, it has an amplitude selected from the group consisting of (xxx) 950-1000V peak-to-peak and (xxx) amplitude exceeding 100V peak-to-peak.

  The high frequency voltage is (i) less than 100 kHz, (ii) 100 to 200 kHz, (iii) 200 to 300 kHz, (iv) 300 to 400 kHz, (v) 400 to 500 kHz, (vi) 0.5 to 1.0 MHz, ( vii) 1.0 to 1.5 MHz, (viii) 1.5 to 2.0 MHz, (ix) 2.0 to 2.5 MHz, (x) 2.5 to 3.0 MHz, (xi) 3.0 to 3.5 MHz, (xii) 3.5-4.0 MHz, (xiii) 4.0-4.5 MHz, (xiv) 4.5-5.0 MHz, (xv) 5.0-5.5 MHz, (xvi ) 5.5-6.0 MHz, (xvii) 6.0-6.5 MHz, (xviii) 6.5-7.0 MHz, (xix) 7.0-7.5 MHz, (xx) 7.5-8 .0MHz, (xxi) 8.0-8.5MHz, xxii) a frequency selected from the group consisting of 8.5 to 9.0 MHz, (xxiii) 9.0 to 9.5 MHz, (xxiv) 9.5 to 10.0 MHz, and (xxv) a frequency exceeding 10.0 MHz. It is preferable to have.

  The ion trap is (i) greater than 0.001 mbar, (ii) greater than 0.01 mbar, (iii) greater than 0.1 mbar, (iv) greater than 1 mbar, (v) greater than 10 mbar, (vi) greater than 100 mbar. A group consisting of (vii) 0.001 to 0.01 mbar, (viii) 0.01 to 0.1 mbar, (ix) 0.1 to 1 mbar, (x) 1 to 10 mbar, and (xi) 10 to 100 mbar. It is preferable to maintain a pressure selected from:

It is a figure which shows the volume theoretically occupied by ion in a three-dimensional ion trap. It is a figure which shows the volume actually occupied by ion in a three-dimensional ion trap. It is a figure which shows the volume theoretically occupied by ion in a two-dimensional ion trap. It is a figure which shows the volume actually occupied by ion in a two-dimensional ion trap. FIG. 3 shows the volume theoretically occupied by ions in a one-dimensional ion trap, according to one embodiment of the invention. FIG. 4 shows the volume actually occupied by ions in a one-dimensional ion trap, according to one embodiment of the invention. FIG. 2 shows a known linear or two-dimensional ion trap with a plurality of annular electrodes surrounding a quadrupole rod set. FIG. 2 shows a known linear or two-dimensional ion trap with a quadrupole rod set with vane electrodes. FIG. 1 shows a known linear or two-dimensional ion trap with a segmented quadrupole rod set. FIG. 3 shows an ion trap according to a preferred embodiment of the present invention. 1 is an end view of a preferred ion trap. FIG. It is a side view of a preferable ion trap. It is a figure which shows the method of confining ion to a x direction within a preferable ion trap by applying a DC voltage to the both ends of an electrode. FIG. 6 is a diagram illustrating a method of confining ions in the x direction within a preferred ion trap by applying a DC voltage to an additional end plate electrode. FIG. 6 is a diagram illustrating a method for confining ions in the x direction within a preferred ion trap by applying a high frequency voltage to an additional rod electrode. FIG. 4 shows a method according to a preferred embodiment in which the DC potential applied to the three groups of electrodes varies along the x direction. It is a figure which shows the method in which direct current potential changes to az direction. It is a figure which shows the three-dimensional display of the DC potential in xy plane. FIG. 5 shows an operating mode in which ion channels are formed in a preferred ion trap. FIG. 4 illustrates a preferred embodiment of the present invention in which ions are selectively propelled in the x-direction of the mass to charge ratio and then ejected from the ion trap in the z-direction of the mass to charge ratio selectively. FIG. 6 shows the results of a SIMION (RTM) simulation that models ion release from a preferred ion trap that did not include space charge effects. It is a figure which shows the result of a SIMION (RTM) simulation when the space charge effect is included. FIG. 6 illustrates one embodiment in which a preferred ion trap is integrated with a stacked annular ion guide (“SRIG”) collision cell. FIG. 2 illustrates an embodiment following an ion source followed by a preferred ion trap, quadrupole and ion detector. FIG. 4 shows an embodiment following an ion source followed by a quadrupole, collision cell, preferred ion trap, another quadrupole and an ion detector. FIG. 4 shows an embodiment following an ion source followed by a preferred ion trap, quadrupole, collision cell, another quadrupole and ion detector. FIG. 2 shows an embodiment following an ion source followed by a preferred ion trap, quadrupole, collision cell and time-of-flight mass analyzer.

  Various embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, along with other arrangements given solely for the purpose of illustration.

  An ion trap according to a preferred embodiment of the present invention is shown in FIG. 3A. The ion trap consists of a three-dimensional array 301 with enlarged electrodes. According to one embodiment, the electrode comprises a segmented rod electrode.

  The ion trap can be considered as comprising two horizontal layers of electrodes. Ions are confined in the vertical (y) direction (ie, between the two horizontal layers of the electrode) by applying a high frequency voltage to the electrode. Ions are confined in the vertical (y) direction by a non-quadrupole pseudopotential.

  FIG. 3B shows an end view of the segmented rod electrode. According to a preferred embodiment, all the segmented electrodes that conceptually form a rod are preferably maintained in the same phase of the high-frequency voltage. The horizontally adjacent segmented rod electrodes are preferably maintained at the opposite high frequency phase. The segmented rod electrodes in the upper layer are preferably maintained at the same high frequency phase as the corresponding segmented rod electrodes in the lower layer.

  Referring to FIG. 3B, ion confinement in the xz plane is preferably achieved by applying the opposite phase of the radio frequency voltage 303 adjacent to the row of electrodes in the x direction.

  FIG. 3C shows a side view of electrode positions that serve to visualize the overall structure.

  The quadrupole DC potential is preferably maintained in the z direction by applying the quadrupole DC potential to the electrodes in the z direction. As a result, the ions are preferably confined within the ion volume 302 shown in FIG. 3A as a cuboid.

  The ions may first enter the ion trap in the z direction and then apply a quadrupole DC potential to the electrodes in the z direction. Alternatively, a quadrupole DC potential may be applied to the electrode in the z direction and ions may enter the ion trap in the x direction.

  Referring to FIGS. 4A-4C, many different techniques may be used to confine ions axially within the ion trap in the x direction.

  FIG. 4A shows a preferred embodiment of the present invention where ions are confined axially within the ion trap in the x direction by applying an auxiliary DC potential 401 to both ends of the electrode in the yz plane or to both outermost portions. According to this embodiment, ions may first enter the ion trap in either the x direction or the z direction.

  FIG. 4B shows an alternative embodiment in which a DC potential may be applied to the additional end plate electrode 402. According to this embodiment, the ions first enter the ion trap via the z direction. Once ions enter the ion trap, the quadrupole potential is then preferably maintained in the z direction.

  FIG. 4C shows another alternative embodiment in which additional segmented rod electrodes or non-segmented rod set electrodes 403 are provided. The high frequency voltage applied to the segmented rod set electrode 301 is also preferably applied to the additional electrode 403 so that ions are confined in the axial direction in the x direction within the ion trap by the pseudopotential barrier or well. According to this embodiment, the ions first enter the ion trap via the z direction. Once ions enter the ion trap, the quadrupole potential is then preferably maintained in the z direction.

  According to a preferred embodiment, it is preferred that the DC quadrupole potential be superimposed on the high frequency voltage applied to the electrode in the z direction so that the DC potential well is formed in the z direction as shown in FIG. 3C. A DC potential may be applied to the electrodes so that the quadrupole potential well is maintained in the z direction before or after ions enter the ion trap.

  The shape of the quadrupole or DC potential well in the z direction preferably varies with the length of the ion trap or along the length of the ion trap.

  Next, an example of how the quadrupole potential may change with or along the length of the ion trap will be described in detail with reference to FIGS.

  FIG. 5A shows a graph of potential applied along the three lines of electrodes labeled 304, 305, 306 in FIG. 3A, the three lines of electrodes having different changes in the z direction. The electrode 304 disposed toward the center of the ion trap may have a low or zero potential gradient in the z-direction, while the electrode 306 disposed farthest from the center of the ion trap may have a high potential gradient. It is clear from FIG. 5A. The effect is to provide an electric field that pours or moves the ions in the z direction toward the center of the ion trap and moves the ions toward one end of the ion trap with zero displacement in the x direction. The magnitude of the electric field in the x direction preferably varies with the position in the z direction, so that the ions cause the ions to accelerate substantially different in the x direction depending on the relative position of the ions in the z direction. Is preferred.

  FIG. 5B shows a graph of the potential applied along the three lines of electrodes labeled 307, 308, 309 in FIG. 3A, where the three lines of electrodes 307, 308, 309 have different displacements in the x direction. An electrode 307 having a displacement closest to zero in the x direction has a narrow quadrupole potential maintained across the electrode in the z direction, while an electrode 309 arranged with a maximum displacement in the x direction is It has a deep quadrupole potential maintained across the electrode in the z direction.

  FIG. 5C shows a three-dimensional graph of the applied potential that serves to visualize the applied potential.

  Embodiments of the present invention are intended to selectively eject ions from a preferred ion trap in one direction in the z direction, either mass or mass to charge ratio. In an alternative embodiment, ions are selectively ejected from the preferred ion trap in the x direction only or in both the x and z directions, either in mass or mass to charge ratio. According to one embodiment, the quadrupole potential maintained in the z-direction may be maintained across most of the electrodes, while a portion of the electrodes on one side of the ion trap is It may be asymmetric in the sense that it may be maintained at a constant potential. As a result, a quadrupole potential is maintained, which effectively truncates one side of the potential well in the z direction. Thus, it will be apparent that the maximum potential on one side of the potential well may be greater than the maximum potential on the other side of the potential well.

  The ion trap according to the preferred embodiment may be used for several different modes of operation.

  In certain modes of operation, the ion trap may be used as an ion transmission device and / or as a collision cell. This can be accomplished by applying an appropriate DC potential to the electrode, so that there is one or more ion permeable channels through which ions pass. FIG. 6A illustrates one embodiment where the ion trap operates as an ion guide and / or as a collision cell.

  FIG. 6B shows a preferred embodiment in which ions are ejected from the ion trap in the z direction. A DC potential is preferably applied to the electrode in the manner shown in the z-direction and as described above in connection with FIG.

  In order to resonately excite ions in the ion trap, it is preferable to apply an AC voltage or a weak voltage (tickling voltage) to the electrodes. It is preferable to vibrate ions in the z direction by applying an alternating voltage or a weak voltage. The amplitude of ion vibration in the z direction is preferably dependent on the mass of the ion or the mass to charge ratio. As discussed above, the electric field causes the ions to face a substantially different acceleration field in the x direction depending on the relative position of the ions in the z direction. Thus, the electric field propels the ion in the x direction with a force that depends on the amplitude of the ion's vibration in the z direction, which in turn depends on the mass or mass to charge ratio of the ion.

  Therefore, when an AC voltage or a weak voltage is applied together with the electric field, ions are transferred from most of the ion trap to a region of the ion trap (ie, toward the left side of the ion trap as shown in FIG. 6B). Preferably) in a manner depending on the mass-to-charge ratio. The ion trap is preferably arranged so that ions cannot be emitted from anywhere other than from a specific ion emission region. The ions are preferably confined in the z-direction by a DC quadrupole potential well, and the height of at least one surface of the well is such that ions having an amplitude of oscillation in the z-direction are located in a region separated from the emission region in the x-direction. Reduced by the position in the x direction towards the emission region to be confined by the ion trap. Ions in the emission region with the same amplitude of oscillation in the z direction can cross the DC potential well and are ejected from the ion trap. The ions emitted from the ion trap may be detected directly or transferred to another radio frequency device and / or mass analyzer for further processing or detection.

  Preferred ion traps have been modeled using the ion optical modeling package SIMION (RTM). FIG. 7A shows graphs of ion release times from preferred ion traps for three groups modeled to have mass-to-charge ratios of 400, 450 and 500 Da. In this example, the space charge effect was ignored. It is clear that ions having a mass to charge ratio of 400 were first released, followed by ions having a mass to charge ratio of 450, followed by ions having a mass to charge ratio of 500.

In order to elucidate the effect of the very large space charge in the ion trap, the same simulation was performed, including approximately 1 × 10 ⁶ charges in the ion trap. As a comparison, it is known that the performance of a conventional three-dimensional ion trap is degraded when the number of charges in the ion trap is approximately 1 × 10 ³ . A considerable number for two-dimensional or linear traps was predetermined to be approximately 5 × 10 ⁴ .

  FIG. 7B shows the release time for a SIMION (RTM) simulation when space charge effects are included. Neither the peak emission time nor the peak width (and hence the ion trap resolution) was unduly affected due to the presence of such a large amount of space charge.

  Thus, as will become apparent from a comparison of FIGS. 7A and 7B, preferred ion traps with expanded ion confinement volumes are particularly advantageous over conventional two-dimensional and three-dimensional ion traps.

  FIG. 8 illustrates another embodiment of the present invention in which a preferred ion trap is integrated with a stacked annular ion guide (“SRIG”) collision cell. The laminated annular ion guide preferably contains argon gas for good fragmentation efficiency, while the preferred ion trap preferably contains helium gas for good emission efficiency. The collision cell and ion trap may be used in conjunction as a single ion transmission and / or collision cell.

  Alternatively, the collision cell and ion trap may be used separately, i.e., the collision cell may be used to fragment and / or stack ions, and the ion trap is stacked on a stacked annular ion guide. May be used to hold and release the generated ions.

  9A-D show examples of equipment arrangements according to various embodiments of the present invention. It will be apparent to those skilled in the art that there are more structural possibilities beyond these examples.

  FIG. 9A shows an embodiment following an ion source, followed by an ion trap according to a preferred embodiment, followed by a quadrupole, followed by an ion detector.

  FIG. 9B shows an embodiment comprising an ion source followed by a quadrupole, followed by a collision cell, followed by an ion trap according to a preferred embodiment, followed by a second quadrupole and an ion detector.

  FIG. 9C shows an embodiment comprising an ion source followed by an ion trap according to a preferred embodiment, followed by a quadrupole, followed by a collision cell, followed by a second quadrupole and an ion detector.

  FIG. 9D shows an embodiment comprising an ion source followed by an ion trap according to a preferred embodiment, followed by a quadrupole, followed by a collision cell and a time-of-flight mass analyzer.

  It will be apparent that various modifications may be made to the specific embodiments discussed above without departing from the scope of the invention.

  For example, it is contemplated that an electrode comprising an ion trap may include an electrode that is not in the form of a rod. For example, the electrode may include a plurality of laminated plate electrodes, a plurality of laminated annular electrodes, and a plurality of laminated semi-annular electrodes of a plurality of C-type electrodes.

  According to a less preferred embodiment, the applied DC potential may be a non-quadrupole.

  According to one embodiment, the DC potential well may have one side of the ion trap deeper than the other side of the ion trap. As a result, ions are preferably emitted in one direction rather than in two directions.

  According to one embodiment, the direction of ions exiting the ion trap is determined by direct current so that all or selected portions of ions preferably exit from one direction, or all or selected portions of ions preferably exit from the other direction. It may be changed by appropriately changing the depth of the well.

  According to one embodiment, the ion trap may be operated in a scan mode coupled to operation that emits mass-to-charge ratio ions from a DC well coupled to an m / z scan of an adjacent mass analyzer.

  According to one embodiment, there may be more than one emission region.

  According to one embodiment, ions may be implanted from one location, may be emitted from the same location, or may be emitted from another spatially different location.

  According to one embodiment, more than one ion compression region may be provided, i.e. ions may be stored in the vane and then moved to the center of the emission region in a mass-to-charge ratio manner.

  Although the present invention has been described with reference to preferred embodiments, various changes in form and detail can be made without departing from the scope of the invention, as set forth in the appended claims. Those skilled in the art will appreciate.

Claims (37)

A first arranged and adapted to generate a radially asymmetric pseudopotential barrier or well that serves to confine ions in a first (y) direction and a second (x) direction within the ion trap. Equipment,
A second device arranged and adapted to generate a substantially quadrupole DC potential well that serves to confine ions in the third (z) direction within the ion trap;
The ions are selectively emitted from the ion emission region of the ion trap in the second (x) direction and / or the third (z) direction so that ions are selectively emitted in a mass or mass-to-charge ratio. A third device arranged and adapted to excite in the direction of (z),
The substantially quadrupole DC potential well profile gradually changes along the second (x) direction so that an electric field is maintained along the second (x) direction. The magnitude of the electric field in the direction of the second (x) varies with the position in the direction of the third (z) so that the ions propel, flow or guide ions toward the ion emission region. And the electric field causes the mass to be exposed to an acceleration field that is substantially different in the second (x) direction, depending on the relative position of the ion in the third (z) direction. Selective ion trap for charge ratio. A pseudopotential barrier or well that acts to confine ions in the first (y) direction within the ion trap and a DC potential barrier or well that acts to confine ions in the second (x) direction are generated. A first device arranged and adapted such that
A second device arranged and adapted to generate a substantially quadrupole DC potential well that serves to confine ions in the third (z) direction within the ion trap;
The ions are selectively emitted from the ion emission region of the ion trap in the second (x) direction and / or the third (z) direction so that ions are selectively emitted in a mass or mass-to-charge ratio. A third device arranged and adapted to excite in the direction of (z),
The substantially quadrupole DC potential well profile gradually changes along the second (x) direction so that an electric field is maintained along the second (x) direction. The magnitude of the electric field in the direction of the second (x) varies with the position in the direction of the third (z) so that the ions propel, flow or guide ions toward the ion emission region. And the electric field causes the mass to be exposed to an acceleration field that is substantially different in the second (x) direction, depending on the relative position of the ion in the third (z) direction. Selective ion trap for charge ratio.   The mass or mass pair according to claim 1 or 2, wherein the first (y) direction and / or the second (x) direction and / or the third (z) direction are substantially orthogonal. Selective ion trap for charge ratio.   4. A mass or mass to charge ratio selective ion trap according to claim 1, 2 or 3, further comprising a plurality of electrodes. The plurality of electrodes are:
(I) Multiple or at least 4, 5, 6, 7, 8, 9, 10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80 -90, 90-100 or more than 100 rod sets or segmented rod sets, multipole rod sets or segmented multipole rod sets, and / or
(Ii) a plurality or at least 4, 5, 6, 7, 8, 9, 10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80 ~ 90, 90-100 or more than 100 annular, ring, or oval electrodes, with one or more apertures through which ions pass through in use, annular, ring, or oval An ion tunnel or ion funnel containing electrodes, and / or
(Iii) a plurality or at least 4, 5, 6, 7, 8, 9, 10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80 ~ 90, 90-100 or more than 100 semi-annular, semi-ring, semi-oval, or C-shaped electrodes, and / or
5. A mass or mass to charge ratio selective ion trap according to claim 4, comprising (iv) a planar electrode, a plate electrode, or a stack or array of planar electrodes or mesh electrodes generally disposed in a plane in which ions travel in use.   6. A mass or mass to charge ratio selective ion trap according to claim 4 or 5, wherein the first device is arranged and adapted to apply a radio frequency voltage to at least some of the electrodes.   The mass according to any one of the preceding claims, wherein the ion trap is arranged and adapted so that there is a solid and / or straight perspective line of the ion trap in the third (z) direction. Or mass-to-charge selective ion trap.   The mass according to any one of claims 1 to 7, wherein the ion trap is arranged and adapted such that there is a solid and / or straight perspective line of the ion trap in the second (x) direction. Or mass-to-charge selective ion trap.   The second device may be (i) such that the minimum of the substantially quadrupole DC potential well is along the central axis of the ion trap or (ii) the substantially quadrupole DC potential well. A mass according to any one of claims 1 to 8, wherein a minimum is arranged and adapted to form the substantially quadrupole DC potential well so as to be offset from the central axis of the ion trap. Selective ion trap with mass-to-charge ratio.   10. The mass or mass to charge ratio selective ion trap according to any one of claims 1 to 9, wherein the pseudopotential barrier or well comprises a non-quadrupole pseudopotential barrier or well.   The third device is arranged and adapted to vibrate ions in the third (z) direction, wherein the amplitude of the ion vibration in the third (z) direction is the mass of the ions or 11. A mass or mass to charge ratio selective ion trap according to any one of the preceding claims, depending on the mass to charge ratio.   The electric field is applied in the third (z) direction before selectively ejecting ions of mass or mass-to-charge ratio in the second (x) direction and / or the third (z) direction. 12. The mass or mass to charge ratio selective ion trap of claim 11, wherein the ions are propelled in the second (x) direction with a force that depends on the amplitude of vibration of the ions.   13. The mass or mass to charge ratio selective ion trap according to any one of claims 1 to 12, wherein the electric field gradually increases or decreases along the second (x) direction.   Ions are confined in the third (z) direction by the quadrupole DC potential well, and ions having vibration amplitude in the third (z) direction are emitted in the second (x) direction in the emission region. Ions in the emission region that are confined by the ion trap in a region away from the other while having the same amplitude of vibration in the third (z) direction can exceed the DC potential well, 14. The height of at least one side of the well decreases with the position in the second (x) direction towards the emission region, so as to be emitted from the ion trap. A selective ion trap of the mass or mass-to-charge ratio of claim 1.   The second device is arranged and adapted to maintain the substantially quadrupole DC potential well across all but not all of the electrodes arranged in the third (z) direction. A selective ion trap of mass or mass to charge ratio according to any one of claims 4, 5 or 6.   The second device is arranged and adapted to maintain a substantially quadrupole DC potential well across x% of the width of the ion trap in a third (z) direction, where x is (I) less than 10, (ii) 10-20, (iii) 20-30, (iv) 30-40, (v) 40-50, (vi) 50-60, (vii) 60-70, (viii) The mass or mass according to any one of claims 1 to 15, selected from the group consisting of: 70-80, (ix) 80-90, (x) 90-95, and (xi) 95-99. Selective ion trap with charge-to-charge ratio.   The second device is arranged and adapted to maintain a direct current potential profile in the third (z) direction across the ion trap, the direct current potential profile comprising the first region and one or more. The DC potential profile in the first region is substantially quadrupole, and the DC potential profile in the one or more second regions is substantially linear. The selective ion trap of mass or mass to charge ratio according to any one of claims 1 to 16, which is constant, non-quadrupole.   18. The second device of claim 1-17, wherein the second device is arranged and adapted to maintain a DC potential profile in the third (z) direction that is asymmetric with respect to a central axis of the ion trap. A selective ion trap of mass or mass-to-charge ratio according to any one of the above.   The second device is arranged and adapted to maintain a DC potential profile in the third (z) direction so that ions are ejected from the substantially quadrupole DC well in only one direction. 19. A selective ion trap of mass or mass to charge ratio according to any one of claims 1-18.   The third device may be configured such that ions from the ion trap are either (i) in the third direction or only in the second direction, or (ii) in either the third direction or the second direction, or 20. A mass or mass to charge ratio selective ion trap according to any one of the preceding claims, arranged and adapted to be selectively released in a mass to charge ratio. 16. The mass according to any one of claims 4, 5, 6, 15 , wherein the third device is arranged and adapted to resonantly excite ions in the third (z) direction. Selective ion trap with mass-to-charge ratio.   The third device is arranged and adapted to apply an auxiliary AC voltage or an auxiliary AC potential to at least some of the electrodes having a frequency σ equal to ω, where ω is an ion that is preferably emitted from the ion trap. The mass or mass to charge ratio selective ion trap of claim 21, wherein the ion trap is a fundamental frequency or resonance frequency of 16. A mass or mass according to any one of claims 4, 5, 6, 15 wherein the third device is arranged and adapted to parametrically excite ions in the third (z) direction. Selective ion trap with charge-to-charge ratio.   The third device has an auxiliary AC voltage or auxiliary AC potential equal to 2ω, 0.667ω, 0.5ω, 0.4ω, 0.33ω, 0.286ω, 0.25ω, or less than 0.25ω. 24. The mass or resonance according to claim 23, arranged and adapted to be applied to at least some of the electrodes having a frequency σ, wherein ω is the fundamental or resonance frequency of ions desired to be ejected from the ion trap. Selective ion trap with mass-to-charge ratio.   The third device is arranged and adapted to scan, change, modify, increase, gradually increase, decrease or gradually decrease the frequency σ of the auxiliary AC voltage or the auxiliary AC potential. 25. A selective ion trap of mass or mass to charge ratio according to claim 22 or 24.   The third device is (i) in an operating mode for ejecting ions from the ion trap in the order of ion mass-to-charge ratio and / or (ii) the ions in the order opposite to the ion mass-to-charge ratio. 26. A mass or mass to charge ratio selective ion trap according to any one of the preceding claims, arranged and adapted to an operating mode for emitting ions from the trap.   27. Selection of mass or mass to charge ratio according to any one of claims 1 to 26, wherein the third device is arranged and adapted to eject ions from the ion trap in a substantially adiabatic manner. Ion trap.   The third device is (i) less than 0.5 eV, (ii) 0.5 to 1.0 eV, (iii) 1.0 to 1.5 eV, (iv) 1.5 to 2.0 eV, (v ) 2.0-2.5 eV, (vi) 2.5-3.0 eV, (vii) 3.0-3.5 eV, (viii) 3.5-4.0 eV, (ix) 4.0-4 Arranged and adapted to emit ions from the ion trap with an ion energy selected from the group consisting of .5 eV, (x) 4.5-5.0 eV, and (xi) greater than 5.0 eV. 28. A selective ion trap of mass or mass to charge ratio according to any one of claims 1-27. Said ion trap, said arranged to include the N ionic charge within the ion trap is adapted, N is (i) 5x10 less than ^{4, (ii) 5x10 4 ~1x10} 5, (iii) 1x10 5 ~2x10 ^{5, (iv) 2x10 5 ~3x10} 5, (v) 3x10 5 ~4x10 5, (vi) 4x10 5 ~5x10 5, (vii) 5x10 5 ~6x10 5, (viii) 6x10 5 ~7x10 5, (ix) ^{7x10 5 ~8x10 5, (x)} 8x10 5 ~9x10 5, (xi) 9x10 5 ~1x10 6 and (xii) is selected from the group consisting of the number of more than 1x10 ^6, any one of claims 1 to 28 A selective ion trap of the mass or mass to charge ratio described in 1. In an operating mode, at least a region or substantially the entire ion trap is
(I) as an ion guide and / or
(Ii) as a collision cell or fragmentation cell and / or
(Iii) as a reaction cell and / or
(Ii) as a mass filter and / or
(Iii) as a time-of-flight separator and / or
(Iv) as an ion mobility separator and / or
30. A mass or mass to charge ratio selective ion trap according to any one of the preceding claims, arranged and adapted to operate as a differential ion mobility separator. In operating mode, the ion trap is (i) less than 1.0 × 10 ⁻⁷ mbar, (ii) 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁶ mbar, (iii) 1.0 × 10 ^{−6 to} 1.0 × 10 ^−5. mbar, (iv) 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻⁴ mbar, (v) 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻³ mbar, (vi) 0.001 to 0.01 mbar, (vii) 0. Arranged to maintain at a pressure selected from the group consisting of 01-0.1 mbar, (viii) 0.1-1 mbar, (ix) 1-10 mbar, (x) 10-100 mbar, and (xi) 100-1000 mbar 31. A mass or mass-to-charge ratio selective ion trap according to any one of claims 1-30.   A mass spectrometer comprising a selective ion trap of mass or mass-to-charge ratio according to any one of claims 1-31. Generating a radially asymmetric pseudopotential barrier or well that serves to confine ions in a first (y) direction and a second (x) direction within the ion trap;
Generating a quadrupole dc potential well substantially confining ions in the third (z) direction within the ion trap, wherein the electric field extends along the second (x) direction. As is maintained, the profile of the substantially quadrupole DC potential well gradually changes along the second (x) direction, and the electric field causes ions to move toward the ion emission region of the ion trap. The magnitude of the electric field in the second (x) direction varies depending on the position in the third (z) direction so that it is propelled, flowed, or guided, and the electric field is depending on the relative position of the ions in the direction of z), causing the ions to face a substantially different acceleration field in the second (x) direction;
Exciting ions in the third (z) direction so as to selectively emit ions of mass or mass-to-charge ratio in the second (x) direction and / or the third (z) direction And selectively releasing ions of mass or mass to charge ratio from the ion trap. A pseudopotential barrier or well that acts to confine ions in the first (y) direction within the ion trap and a DC potential barrier or well that acts to confine ions in the second (x) direction are generated. And
Generating a quadrupole dc potential well substantially confining ions in the third (z) direction within the ion trap, wherein the electric field extends along the second (x) direction. As is maintained, the profile of the substantially quadrupole DC potential well gradually changes along the second (x) direction, and the electric field causes ions to move toward the ion emission region of the ion trap. The magnitude of the electric field in the second (x) direction varies depending on the position in the third (z) direction so that it is propelled, flowed, or guided, and the electric field is depending on the relative position of the ions in the direction of z), causing the ions to face a substantially different acceleration field in the second (x) direction;
Exciting ions in the third (z) direction so as to selectively emit ions of mass or mass-to-charge ratio in the second (x) direction and / or the third (z) direction And selectively releasing ions of mass or mass to charge ratio from the ion trap.   35. A method of mass spectrometry comprising the method of claim 33 or 34. A first arranged and adapted to generate a radially asymmetric pseudopotential barrier or well that serves to confine ions in a first (y) direction and a second (x) direction within the ion trap. Equipment,
A second device arranged and adapted to generate a substantially quadrupole DC potential well that serves to confine ions in the third (z) direction within the ion trap;
A third device arranged and adapted to vibrate ions in the third (z) direction, wherein the amplitude of the vibration of the ions in the third (z) direction is the mass of the ions Or a third device, depending on the mass to charge ratio,
As an electric field is maintained along the direction of the first 2 (x), the profile of the substantially quadrupole DC potential is gradually changed along the direction of the first 2 (x), ion-release Prior to selectively ejecting the ions in mass or mass to charge ratio from the region in the second (x) direction and / or in the third (z) direction, the electric field is toward the ion emitting region of the ion trap with a force that depends on the amplitude of oscillation of the ions in the direction, the direction in to propel the ions of the first 2 (x), in the direction of the first 2 (x) The ion or mass-to-charge selective ion trap, wherein the magnitude of the electric field varies with position in the third (z) direction. Arranged and adapted to generate a pseudopotential barrier or well that acts to confine ions in the first (y) direction and a DC potential barrier or well that acts to confine ions in the second (x) direction within the ion trap. A first device,
A second device arranged and adapted to generate a substantially DC quadrupole potential well that serves to confine ions in the third (z) direction within the ion trap;
A third device arranged and adapted to vibrate ions in the third (z) direction, wherein the amplitude of the vibration of the ions in the third (z) direction is the mass of the ions Or a third device, depending on the mass to charge ratio,
As an electric field is maintained along the direction of the first 2 (x), the profile of the substantially quadrupole DC potential is gradually changed along the direction of the first 2 (x), ion-release Prior to selectively ejecting the ions in mass or mass to charge ratio from the region in the second (x) direction and / or in the third (z) direction, the electric field is toward the ion emitting region of the ion trap with a force that depends on the amplitude of oscillation of the ions in the direction, the direction in to propel the ions of the first 2 (x), in the direction of the first 2 (x) The ion or mass-to-charge selective ion trap, wherein the magnitude of the electric field varies with position in the third (z) direction.

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